CN107213889A

CN107213889A - Blending method prepares molybdenum base and tungsten base fluorine chlorine exchange catalysts

Info

Publication number: CN107213889A
Application number: CN201710255937.7A
Authority: CN
Inventors: 权恒道; 张呈平; 庆飞要; 刘冬鹏
Original assignee: BEIJING YUJI TECHNOLOGY DEVELOPMENT Co
Current assignee: Quanzhou Yuji New Material Technology Co.,Ltd.
Priority date: 2017-04-18
Filing date: 2017-04-18
Publication date: 2017-09-29
Anticipated expiration: 2037-04-18
Also published as: CN107213889B

Abstract

The present invention relates to " blending method prepares molybdenum base and tungsten base fluorine chlorine exchange catalysts ", belong to the field of chemical synthesis.The non-chrome catalysts of the present invention are made up of non-chromium ion and auxiliary agent, and the weight/mass percentage composition of non-chromium ion and auxiliary agent is followed successively by 60%~100% and 0~40%, wherein, non- chromium ion is the one or several kinds in divalence tungsten ion, trivalent tungsten ion, tetravalence tungsten ion, pentavalent tungsten ion, sexavalence tungsten ion, divalence molybdenum ion, trivalent molybdenum ion, tetravalence molybdenum ion, pentavalent molybdenum ion, sexavalence molybdenum ion, and auxiliary agent is other metallic elements.Catalyst of the present invention is passed through hydrogen fluoride gas in activation stage, an oxide part for non-chromium ion is converted into the oxyfluoride of non-chromium ion.The non-chrome catalysts temperature in use of the present invention is high, catalytic activity is high, service life is long, is mainly used in gas phase catalysis alkenyl halide generation exchange chloride for fluoride under high temperature and prepares Fluorine containing olefine.

Description

Blending method prepares molybdenum base and the fluoro- chlorine exchange catalysts of tungsten base

Technical field

The present invention relates to a kind of non-chrome catalysts, occur fluoro- chlorine more particularly, to gas phase catalysis alkenyl halide under high temperature and hand over Change catalyst with base of molybdenum and tungsten-based catalyst that reaction prepares Fluorine containing olefine.

Background technology

In order to fulfil the Montreal Agreement for the ozone layer that is intended to preserve our planet, the hydrogen of zero odp value has been released in countries in the world Fluorohydrocarbon (HFCs) and HF hydrocarbon (HFOs), so as to eliminate CFC (CFCs) and hydrogen fluorochlorohydrocarbon that ODP values are not zero (HCFCs).At present, HFCs and HFOs have been widely used as refrigerant, cleaning agent, foaming agent, extinguishing chemical, etching agent etc..

At present, industrial production HFCs or HFOs uses the fluoro- chlorine exchange reaction of gas phase catalysis of halogenated organic matters mostly Method, the method has the advantages that technique is simple, is easy to continuous large-scale production, safe operation.Urged in the gas phase of halogenated organic matters It is fluoro- chlorine exchange catalysts to change played the role of a nucleus in fluoro- chlorine exchange reaction.At present, common fluoro- chlorine exchange catalysts are chromium Base catalyst, its main active component is chromium.

Du pont company reports the element modified chromium-based catalysts of Al in patent US4465786, for being catalyzed system Standby trifluoro propene.

It is that raw material exists that du pont company reports monochloromonofluoromethane with tetrafluoropropene in patent US20100051853 Reacted under aluminum halide effect and obtain 1- chloro- 2,2,3,3,3- pentafluoropropanes (HCFC-235cb), then HCFC-235cb exists Cr₂O₃In the presence of occur dehydrofluorination and obtain E/Z-1- chloro- 2,3,3,3- tetrafluoropropenes (E/Z-HCFC-1224yd), finally Under the element modified chromium-based catalysts effects of Zn with hydrogen fluoride the fluoro- chlorine exchange reaction of gas phase occurs for E/Z-HCFC-1224yd, obtains To E/Z-1,1,1,2,3- pentafluoropropene (E/Z-HFC-1225ye), trans and cis-configuration content is respectively 95%, 5%.

The chromium-based catalysts that Imperial Chemical Industries of Britain report the modification of Zn elements in patent US5763704 are used Difluoromethane (HFC-32) is prepared in catalysis.

Imperial Chemical Industries of Britain report the chromium that Zn elements and Ni elements are modified jointly in patent US5763707 Base catalyst, which is used to be catalyzed, prepares HFC-125.

French Ai Erfu Atochem (FR) Cedex 22, 94091 Paris La Defense, France reports chromium-based catalysts catalysis HCO-1233za in patent US5811603 Prepare 1- chloro-3,3,3 ,-trifluoropropenes (HCFO-1233zd), 1,3,3,3- tetrafluoropropenes (HFO-1234ze) and 1,1,1,3,3- Pentafluoropropane (HFC-245fa).

French Ai Erfu Atochem (FR) Cedex 22, 94091 Paris La Defense, France reports what Al elements and Ni elements were modified jointly in patent US6184172 Chromium-based catalysts are used to be catalyzed 1- chloro- 3, and 3,3- HFC-143as (HCFC-133a) prepare 1,1,1,3- HFC-134a (HFC- 134a)。

Daikin company reports a kind of specific surface area S=170-300m in patent US6300531²/ g chromium base is urged Agent, occurs fluoro- chlorine exchange reaction synthesis HFC-134a, it can also be used to be catalyzed tetrachloro-ethylene for being catalyzed 1,1,1- trichloroethanes Generation exchange chloride for fluoride obtains pentafluoroethane (HFC-125).

Daikin company reports chromium-based catalysts catalysis 2- chloro- 3,3,3- trifluoros in patent US20130217928 Propylene (HCFO-1233xf) occurs the fluoro- chlorine exchange reaction of gas phase with HF and obtains 2,3,3,3- tetrafluoropropenes (HFO-1234yf).

Japanese Central glass companies report chromium-based catalysts in patent US5905174 to be used to be catalyzed pentachloro- third Ketone prepares the fluoro- 3,3- dichloroacetones of 1,1,1- tri-.

Nippon Zeon Co., Ltd. and Central Glass CO., Ltd. report a kind of fluoro- chlorine exchange in patent CN1192995C and urged Agent, using infusion process by Cr (NO₃)₃It is carried on activated carbon, obtains, at 330 DEG C, use through drying, roasting, hydrogen fluoride activation In catalysis cyclo-CF₂CF₂CF₂CCl=CCl occurs fluoro- chlorine exchange reaction with hydrogen fluoride and prepares cyclo-CF₂CF₂CF₂CF= CCl, its catalytic activity is very low, and conversion ratio is only 26%, and selectivity is 91%.

Chinese Co., Ltd of Jinzhu Modern Chemical Co., Ltd., Xi'an is reported in patent CN1408476 in Mn, Co or Zn A kind of another element in element, and Mg or Ni, totally two kinds of element modified chromium-based catalysts be used to be catalyzed trichloro ethylene, Through intermediate HCFC-133a, occurs the fluoro- chlorine exchange reaction synthesis HFC-134a of two step gas phases.

Chinese Sinochem Modern Environmental Protection Chemicals (Xi'an) Co., Ltd. reports rare earth element in patent CN102580767A Modified chromium-based catalysts, which are used to being catalyzed HCFC-133a and HF the generation fluoro- exchange reaction of gas phase, synthesizes HFC-134a.

Chinese Xi'an Inst. of Modern Chemistry reports cobalt and magnesium-modified chrome catalysts in patent CN1145275, carries Body is aluminum fluoride, for being catalyzed trichloro ethylene, through intermediate HCFC-133a, occurs the fluoro- chlorine exchange reaction synthesis of two step gas phases HFC-134a.Chromium-based catalysts once caused grinding for countries in the world scientist due to the advantage that its raw material is easy to get, activity is higher Study carefully interest.But going deep into research, it has been found that, chrome catalysts still have that temperature in use is low, catalytic activity is low, use Short life, the defect for being difficult to recycling, and more importantly chromium has toxicity, can be special to artificial into great damage It is not that high valence chrome has strong carcinogenicity.Research thinks that Cr VI is higher than trivalent chromium toxicity 100 times, and be easily absorbed by the body and Accumulation in vivo, the speed that it is metabolized and is eliminated is slow.Under certain condition, trivalent chromium and Cr VI can be converted mutually.Six Valency chromium can cause the mankind to suffer from respiratory cancer by confirmation.Cr VI once absorbed by intracellular ubiquitous reducing agent and It is metabolized, then the cell of the digestive system of the mankind can then form the cancer of the DNA damage of chromium promotion.Cr VI is by the World Health Organization IARC (IARC) is classified as " human carcinogen ".

The content of the invention

To be solved by this invention is the non-chromium-based catalysts that always search for of people as fluoro- chlorine exchange catalysts.Hair A kind of bright safety and environmental protection of catalyst offer is harmless, catalytic activity is high, the non-chrome catalysts of service life length.This invention is in gas Fluoro- chlorine exchange reaction is mutually catalyzed, there is milestone effect in terms of finding non-chromium-based catalysts.

Another technical problem to be solved by this invention is to provide a kind of preparation method of above-mentioned non-chrome catalysts.

A kind of non-chrome catalysts, are made up of non-chromium ion and auxiliary agent, the non-chromium ion be divalence tungsten ion, trivalent tungsten from Son, tetravalence tungsten ion, pentavalent tungsten ion, sexavalence tungsten ion, divalence molybdenum ion, trivalent molybdenum ion, tetravalence molybdenum ion, pentavalent molybdenum from Son, the one or several kinds in sexavalence molybdenum ion, auxiliary agent be Al, Mg, Ni, Co, Ti, Zr, V, Fe, Zn, In, Cu, Ag, Cd, Hg, At least one of Ga, Sn, Pb, Mn, Ba, Re, Sc, Sr, Ru, Nb, Ta, Ca, Ce, Sb, Tl, Hf or several, and non-chromium ion Quality percentage composition with auxiliary agent is 60%~100% and 0~40%, and the preparation method of the catalyst is as follows：

(1) according to the mass percent of non-chromium ion and auxiliary agent, the precursor of the precursor of non-chromium ion and auxiliary agent is mixed equal It is even, it is compressing, obtain catalyst precarsor；

(2) catalyst precarsor for obtaining step (1), carries out roasting 6~15 in 300 DEG C~500 DEG C under nitrogen atmosphere Hour；It is 1 in the amount ratio of material in 200 DEG C~400 DEG C：2 hydrogen fluoride and the mixed gas activation 6~15 that nitrogen is constituted are small Shi Hou, is made non-chrome catalysts.

The precursor of the non-chromium ion is wolframic acid, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, three two tungsten of oxidation, titanium dioxide Tungsten, tungsten pentoxide, dihydro tungsten oxide, three hydroxide tungsten, tungsten tetrahydroxide, pentahydro- tungsten oxide, hexahydro tungsten oxide, three oxidations two Molybdenum, molybdenum dioxide, molybdenum hemipentoxide, molybdenum trioxide, two molybdenum hydroxides, molybdenum trihydroxide, four molybdenum hydroxides, five molybdenum hydroxides, At least one of hexahydro molybdenum oxide, positive ammonium molybdate, ammonium dimolybdate, ammonium tetramolybdate or ammonium heptamolybdate are several, before auxiliary agent Body is at least one of oxide, hydroxide, nitrate, acetate or carbonate of metal or several.

The preferred ammonium metatungstate of precursor or ammonium dimolybdate of the non-chromium ion, the precursor of the auxiliary agent is containing manganese or scandium or rhenium Or the compound of nickel or cobalt, the weight/mass percentage composition of non-chromium ion and assistant metal element is followed successively by 80%~95% and 5~ 20%.

The precursor of the auxiliary agent is the nitrate of metal.

The precursor of the non-chrome catalysts is the mixture of ammonium metatungstate and nickel nitrate, wherein, tungsten ion and nickel element Mass percent composition is 90% and 10%；Or

The precursor of described non-chrome catalysts is the mixture of ammonium metatungstate and scandium nitrate, wherein, tungsten ion and scandium element Mass percent composition be 90% and 10%；Or

The precursor of described non-chrome catalysts be ammonium metatungstate and the mixture with nitric acid rhenium, wherein, tungsten ion and rhenium member The mass percent composition of element is 90% and 10%；Or

The preferred ammonium dimolybdate of precursor and the mixture of nickel nitrate of described non-chrome catalysts, wherein, molybdenum ion and nickel member The mass percent of element is 90% and 10%；Or

The preferred ammonium dimolybdate of precursor and the mixture of cobalt nitrate of described non-chrome catalysts, wherein, molybdenum ion and cobalt member The mass percent of element is 90% and 10%.

The preparation method of above-mentioned non-chrome catalysts, using the following steps：

Application of the above-mentioned non-chrome catalysts in exchange chloride for fluoride.

The exchange chloride for fluoride is high temperature gas phase reaction, and wherein raw material is chloride alkenyl halide, and product is Fluorine containing olefine And hydrogen fluoride gas, the pyroreaction is 300 DEG C -450 DEG C.

The pyroreaction is preferably 400-450 DEG C.

The alkenyl halide is cyclo-CF₂CF₂CF₂CCl=CCl, prepares cyclo-CF₂CF₂CF₂CF=CCl；

Or the alkenyl halide is 2- chloro-3,3,3 ,-trifluoropropenes (being abbreviated as HCFO-1233xf), prepares 2,3,3,3- Tetrafluoropropene (is abbreviated as HFO-1234yf)；

Or the alkenyl halide is E/Z-1- chloro- 2,3,3,3- tetrafluoropropenes prepare E/Z-1,2,3,3,3- five fluorine third Alkene (is abbreviated as E/Z-HFO-1225ye)；

Or the alkenyl halide is E-1- chloro-3,3,3 ,-trifluoropropenes, prepares E/Z-1,3,3,3- tetrafluoropropenes (are write a Chinese character in simplified form For E/Z-HFO-1234ze)；

Or the alkenyl halide is Z-1- chloro-3,3,3 ,-trifluoropropenes, prepares E/Z-HFO-1234ze.

The present invention prepares catalyst using blending method, by the precursor of the precursor of non-chromium ion and auxiliary agent according to certain ratio Catalyst precarsor is mixed to prepare, when precursor is through high-temperature roasting, compound (such as acid, ammonium salt, hydroxide) hair of non-chromium ion Heat solution obtains the oxide of non-chromium ion, and the precursor (hydroxide, nitrate, acetate or carbonate) of auxiliary agent can be with Pyrolysis obtains the oxide of auxiliary agent, and then the precursor of the catalyst enters the activation for the mixed gas being made up of hydrogen fluoride and nitrogen In the stage, it is fluorinated as most of oxide of auxiliary agent as metal fluoride, is still that oxide form is present on a small quantity, rather than An oxide part for chromium ion can react with hydrogen fluoride, and detailed process is as follows：

(1) when the oxide of tungsten is tungstic acid, occur following react：WO₃+4HF→H₂[WO₂F₄]+H₂O↑。

(2) when the oxide of tungsten is a tungsten oxide, three two tungsten of oxidation, tungsten dioxide or tungsten pentoxide, can also occur Similar to the reaction of (1), the fluorine oxidation wolframic acid of corresponding trivalent tungsten ion, tetravalence tungsten ion or pentavalent tungsten ion is generated.

(3) when the oxide of molybdenum is molybdenum trioxide, occur following react：2MoO₃+12HF→H₂[MoF₈]+H₂[MoO₂F₄]+ 4H₂O↑。

(4) when the oxide of molybdenum is molybdenum monoxide, molybdenum sesquioxide, molybdenum dioxide or molybdenum hemipentoxide, can also occur Similar to the reaction of (3), the fluorination of corresponding divalence molybdenum ion, trivalent molybdenum ion, tetravalence molybdenum ion or pentavalent molybdenum ion is generated Molybdic acid or molybdenum oxyfluoride acid.

In the activation stage of above-mentioned hydrogen fluoride, non-chromium ion is main with from divalence to the non-chromium ion of sexavalence different valence state Oxide and oxyfluoride are present.Because the oxide of non-chromium ion has strong lewis acid, the fluorine of particularly non-chromium ion Oxide has highly acid, causes non-chrome catalysts to have strong catalytic activity, along with other metallic elements are as auxiliary agent, increases The strong stability of non-chrome catalysts.Whole effect sees, the non-chrome catalysts prepared by such scheme not only temperature in use Height, and catalytic activity is high, service life is long.

The non-chrome catalysts of the present invention prepare fluorine-containing suitable for the fluoro- chlorine exchange reaction of high temperature gas phase catalysis alkenyl halide generation Alkene.Wherein, starting halo alkene can contain fluorine atom, can also not contain fluorine atom, but must contain and remove fluorine atom And the one or several kinds in outer other halogen atoms such as chlorine atom or bromine atoms or iodine atom.For example：cyclo-CF₂CF₂CF₂CCl =CCl gas phase catalytic fluorinations prepare cyclo-CF₂CF₂CF₂CF=CCl, 2- chloro-3,3,3 ,-trifluoropropene (are abbreviated as HCFO- 1233xf) gas phase catalytic fluorination prepares 2,3,3,3- tetrafluoropropenes (being abbreviated as HFO-1234yf), E/Z-1- chloro- 2,3,3,3- tetra- Fluoropropene (being abbreviated as E/Z-HCFO-1224yd) gas phase catalytic fluorination prepares E/Z-1,2,3,3,3- pentafluoropropenes and (is abbreviated as E/ Z-HFO-1225ye), E-1- chloro-3,3,3 ,-trifluoropropenes gas phase catalytic fluorination prepares E/Z-1, and 3,3,3- tetrafluoropropenes (are write a Chinese character in simplified form For E/Z-HFO-1234ze), Z-1- chloro-3,3,3 ,-trifluoropropenes gas phase catalytic fluorination prepares E/Z-HFO-1234ze etc..

The present invention compared with prior art, has the advantage that as follows：

(1) so far, sufficient information not yet determines whether that suction, oral or skin touch tungsten or tungsten his thing meeting Cause the generation of human cancer.U.S. sanitary and crowd service department (the Department of Health and Human Services, DHHS), IARC (the International Agency for Research on Cancer, IARC) or Environmental Protection Agency (the Environmental Protection Agency, U.S.EPA) is all still Tungsten is not classified as with carcinogenicity.In addition, for the mankind, molybdenum be in second, third class transition elements it is known it is unique must to people Indispensable element, compared with similar transition elements, the toxicity of molybdenum is extremely low, or even is believed that substantially nontoxic.Research discovery, soil Containing the area that molybdenum is too high, cancer morbidity is relatively low.Therefore, compared with chromium-based catalysts, non-chrome catalysts of the invention have peace Entirely, environmentally friendly, harmless the characteristics of.

(2) non-chrome catalysts are when the mixed gas being made up of hydrogen fluoride and nitrogen is activated, the oxide one of non-chromium ion Part can react the oxyfluoride of the non-chromium ion for obtaining highly acid with HF, cause non-chrome catalysts to have stronger catalysis Activity, and non-chrome catalysts are modified by metallic element, substantially increase the stability of non-chrome catalysts.

(3) non-chrome catalysts of the invention are applied to the fluoro- chlorine exchange reaction system of gas phase catalysis alkenyl halide generation under high temperature Standby Fluorine containing olefine, temperature in use is up to 450 DEG C, hence it is evident that more much higher than 330 DEG C of the prior art.

Embodiment

Below by embodiment, the present invention is described in more detail, but is not limited to given example.

Analytical instrument：Shimadzu GC-2010, chromatographic column is DB-VRX capillary column (i.d.0.32mm； length30m；J&W Scientific Inc.).

GC analysis methods：Reaction product takes gaseous sample to carry out GC analyses after washing, alkali cleaning and drying.Detector temperature 250 DEG C of degree, 250 DEG C of temperature of vaporization chamber, 40 DEG C of post initial temperature is kept for 10 minutes, and 15 DEG C/min is warming up to 230 DEG C, is kept for 8 minutes.

Embodiment 1

It is 90% and 10% according to the percentage composition of tungsten ion and manganese element, ammonium metatungstate is uniformly mixed with manganese nitrate Close, compression molding, catalyst precarsor is made, catalyst precarsor 10mL is loaded to 1/2 inch of internal diameter, long 30cm Monel material Tubular reactor, be passed through nitrogen 450 DEG C be calcined 8 hours, nitrogen air speed be 200h^-1, 300 DEG C are then cooled to, is led to simultaneously The amount ratio for entering material is 1：The mixed gas that 2 hydrogen fluoride is constituted with nitrogen, the total air speed of gas is 220h^-1, activate 12 hours, stop Only above-mentioned mixed gas, is made non-chrome catalysts.

Embodiment 2

The preparation technology of catalyst is substantially the same manner as Example 1, except that the percentage group of tungsten ion and manganese element As 100% and 0.

Embodiment 3

The preparation technology of catalyst is substantially the same manner as Example 1, except that the percentage group of tungsten ion and manganese element As 80% and 20%.

Embodiment 4

The preparation technology of catalyst is substantially the same manner as Example 1, except that the percentage group of tungsten ion and manganese element As 70% and 30%.

Embodiment 5

The preparation technology of catalyst is substantially the same manner as Example 1, except that the percentage group of tungsten ion and manganese element As 60% and 40%.

Embodiment 6

The preparation technology of catalyst is substantially the same manner as Example 1, except that ammonium metatungstate is changed to ammonium paratungstate, tungsten from The percentage composition of son and manganese element is 90% and 10%.

Embodiment 7

The preparation technology of catalyst is substantially the same manner as Example 1, except that ammonium metatungstate is changed to ammonium tungstate, tungsten ion Percentage composition with manganese element is 90% and 10%.

Embodiment 8

The preparation technology of catalyst is substantially the same manner as Example 1, except that being adjusted by secondary tungsten acid ammonium solution with hydrochloric acid PH value<1, wolframic acid is obtained, then through 80 DEG C of dehydrations, dry, crushing, obtain wolframic acid H₂WO₄, the percentage group of tungsten ion and manganese element Turn into.

Embodiment 9

The preparation technology of catalyst is substantially the same manner as Example 1, except that ammonium metatungstate is changed to tungstic acid, tungsten from The percentage of son and manganese element is constituted.Wherein, tungstic acid can (wolframic acid can be according to wolframic acid in embodiment 8 by wolframic acid It is prepared by preparation method) it is dehydrated and obtains at more than 100 DEG C.

Embodiment 10

The preparation technology of catalyst is substantially the same manner as Example 1, except that ammonium metatungstate is changed to tungsten dioxide, tungsten from The percentage composition of son and manganese element is 90% and 10%.

Embodiment 11

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to aluminum nitrate, tungsten ion and The percentage composition of aluminium element is 90% and 10%.

Embodiment 12

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to magnesium nitrate, tungsten ion and The percentage composition of magnesium elements is 90% and 10%.

Embodiment 13

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to nickel nitrate, tungsten ion and The percentage composition of nickel element is 90% and 10%.

Embodiment 14

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to cobalt nitrate, tungsten ion and The percentage composition of cobalt element is 90% and 10%.

Embodiment 15

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to Titanium Nitrate, tungsten ion and The percentage composition of titanium elements is 90% and 10%.

Embodiment 16

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to zirconium nitrate, tungsten ion and The percentage composition of zr element is 90% and 10%.

Embodiment 17

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to nitric acid vanadium acyl, tungsten ion Percentage composition with v element is 90% and 10%.

Embodiment 18

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to ferric nitrate, tungsten ion and The percentage composition of ferro element is 90% and 10%.

Embodiment 19

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to zinc nitrate, tungsten ion and The percentage composition of Zn-ef ficiency is 90% and 10%.

Embodiment 20

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to indium nitrate, tungsten ion and The percentage composition of phosphide element is 90% and 10%.

Embodiment 21

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to copper nitrate, tungsten ion and The percentage composition of copper is 90% and 10%.

Embodiment 22

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to silver nitrate, tungsten ion and The percentage composition of silver element is 90% and 10%.

Embodiment 23

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to cadmium nitrate, tungsten ion and The percentage composition of cadmium element is 90% and 10%.

Embodiment 24

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to mercuric nitrate, tungsten ion and The percentage composition of mercury element is 90% and 10%.

Embodiment 25

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to gallium nitrate, tungsten ion and The percentage composition of gallium element is 90% and 10%.

Embodiment 26

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to nitric acid tin, tungsten ion and The percentage composition of tin element is 90% and 10%.

Embodiment 27

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to plumbi nitras, tungsten ion and The percentage composition of lead element is 90% and 10%.

Embodiment 28

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to strontium nitrate, tungsten ion and The percentage composition of strontium element is 90% and 10%.

Embodiment 29

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to barium nitrate, tungsten ion and The percentage composition of barium element is 90% and 10%.

Embodiment 30

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to nitric acid rhenium, tungsten ion and The percentage composition of rhenium element is 90% and 10%.

Embodiment 31

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to scandium nitrate, tungsten ion and The percentage composition of scandium element is 90% and 10%.

Embodiment 32

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to nitric acid ruthenium, tungsten ion and The percentage composition of ruthenium element is 90% and 10%.

Embodiment 33

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to nitric acid niobium, tungsten ion and The percentage composition of niobium element is 90% and 10%.

Embodiment 34

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to nitric acid tantalum acyl, tungsten ion Percentage composition with tantalum element is 90% and 10%.

Embodiment 35

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to calcium nitrate, tungsten ion and The percentage composition of calcium constituent is 90% and 10%.

Embodiment 36

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to cerous nitrate, tungsten ion and The percentage composition of Ce elements is 90% and 10%.

Embodiment 37

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to nitric acid antimony, tungsten ion and The percentage composition of antimony element is 90% and 10%.

Embodiment 38

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to thallium nitrate, tungsten ion and The percentage composition of thallium element is 90% and 10%.

Embodiment 39

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to hafnium nitrate, tungsten ion and The percentage composition of hafnium element is 90% and 10%.

Embodiment 40

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to manganese oxide, tungsten ion and The percentage composition of manganese element is 90% and 10%.

Embodiment 41

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to manganous hydroxide, tungsten ion Percentage composition with manganese element is 90% and 10%.

Embodiment 42

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to manganese acetate, tungsten ion and The percentage composition of manganese element is 90% and 10%.

Embodiment 43

The preparation technology of catalyst is substantially the same manner as Example 1, except that ammonium metatungstate is changed to the tungsten of three oxidation two, tungsten The percentage composition of ion and manganese element is 90% and 10%.

Embodiment 44

The preparation technology of catalyst is substantially the same manner as Example 1, except that ammonium metatungstate is changed to tungsten pentoxide, tungsten The percentage composition of ion and manganese element is 90% and 10%.

Embodiment 45

It is 90% and 10% according to the percentage composition of molybdenum ion and nickel element, ammonium dimolybdate is uniformly mixed with nickel nitrate Close, compression molding, catalyst precarsor is made, catalyst precarsor 10mL is loaded to 1/2 inch of internal diameter, long 30cm Monel material Tubular reactor, be passed through nitrogen 450 DEG C be calcined 8 hours, nitrogen air speed be 200h^-1, 300 DEG C are then cooled to, is led to simultaneously The amount ratio for entering material is 1：The mixed gas that 2 hydrogen fluoride is constituted with nitrogen, the total air speed of gas is 220h^-1, activate 12 hours, stop Only above-mentioned mixed gas, is made catalyst with base of molybdenum.

Embodiment 46

The preparation technology of catalyst and embodiment 45 are essentially identical, except that the percentage group of molybdenum ion and nickel element As 100% and 0.

Embodiment 47

The preparation technology of catalyst and embodiment 45 are essentially identical, except that the percentage group of molybdenum ion and nickel element As 80% and 20%.

Embodiment 48

The preparation technology of catalyst and embodiment 45 are essentially identical, except that the percentage group of molybdenum ion and nickel element As 70% and 30%.

Embodiment 49

The preparation technology of catalyst and embodiment 45 are essentially identical, except that the percentage group of molybdenum ion and nickel element As 60% and 40%.

Embodiment 50

The preparation technology of catalyst and embodiment 45 are essentially identical, except that ammonium dimolybdate is changed to positive ammonium molybdate, molybdenum The percentage composition of ion and nickel element is 90% and 10%.

Embodiment 51

The preparation technology of catalyst and embodiment 45 are essentially identical, except that ammonium dimolybdate is changed to ammonium tetramolybdate, molybdenum The percentage composition of ion and nickel element is 90% and 10%.

Embodiment 52

The preparation technology of catalyst and embodiment 45 are essentially identical, except that ammonium dimolybdate is changed to ammonium heptamolybdate, molybdenum The percentage composition of ion and nickel element is 90% and 10%.

Embodiment 53

The preparation technology of catalyst and embodiment 45 are essentially identical, except that ammonium dimolybdate is changed to molybdic acid, molybdenum ion Percentage composition with nickel element is 90% and 10%.

Embodiment 54

The preparation technology of catalyst and embodiment 45 are essentially identical, except that ammonium dimolybdate is changed to molybdenum trioxide, molybdenum The percentage composition of ion and nickel element is 90% and 10%.

Embodiment 55

The preparation technology of catalyst and embodiment 45 are essentially identical, except that ammonium dimolybdate is changed to molybdenum dioxide, molybdenum The percentage composition of ion and nickel element is 90% and 10%.

Embodiment 56

The preparation technology of catalyst and embodiment 45 are essentially identical, except that ammonium dimolybdate is changed to molybdenum sesquioxide, The percentage composition of molybdenum ion and nickel element is 90% and 10%.

Embodiment 57

The preparation technology of catalyst and embodiment 45 are essentially identical, except that ammonium dimolybdate is changed to molybdenum hemipentoxide, The percentage composition of molybdenum ion and nickel element is 90% and 10%.

Embodiment 58

The preparation technology of catalyst and embodiment 45 are essentially identical, except that nickel nitrate is changed to cobalt nitrate, molybdenum ion Percentage composition with cobalt element is 90% and 10%.

Application examples 1

Fluoro- chlorine exchange catalysts prepared by embodiment 1, the reaction for following synthesis series fluorosurfactants alkene：

(1)

(2)

(3)

(4)

(5)

After reaction 20 hours, after reaction product removes HF through washing, alkali cleaning, constituted with GC analyzing organic substances, as a result such as the institute of table 1 Show.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 1

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	43.4	91.3
(1)	330	10：1	15	26.6	92.8
						(2)	360	4：1	16	85.7	84.7
(2)	330	4：1	16	53.4	78.2
						(3)	320	8：1	30	65.1	86.3
(3)	300	8：1	30	50.5	89.0
						(4)	450	10：1	6	86.2	90.5
(4)	400	10：1	6	80.0	78.7
						(5)	450	10：1	6	86.0	88.9
(5)	400	10：1	6	80.7	75.1

Fluorine containing olefine selectively refers to the ratio of target product, and generation E-HFO-1225ye, Z-HFO- are referred to for reaction (3) 1225ye selective summation, the selectivity for referring to generation E-HFO-1234ze, Z-HFO-1234ze for reaction (4) and (5) is total With, other reaction be simple target product selectivity.

Application examples 2

Catalyst prepared by embodiment 2 is used for the reaction for synthesizing series fluorosurfactants alkene, and application conditions and application examples 1 are basic It is identical, as a result as shown in table 2.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 2

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	28.8	91.4
(1)	330	10：1	15	13.2	93.1
						(2)	360	4：1	16	48.1	69.6
(2)	330	4：1	16	23.7	68.3
						(3)	320	8：1	30	49.4	86.4
(3)	300	8：1	30	24.7	88.8
						(4)	450	10：1	6	68.8	90.9
(4)	400	10：1	6	58.0	78.6
						(5)	450	10：1	6	66.1	88.6
(5)	400	10：1	6	59.3	75.2

Application examples 3

Catalyst prepared by embodiment 3 is used for the reaction for synthesizing series fluorosurfactants alkene, and application conditions and application examples 1 are basic It is identical, as a result as shown in table 3.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 3

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	39.2	90.7
(1)	330	10：1	15	22.3	92.2
						(2)	360	4：1	16	71.5	69.6
(2)	330	4：1	16	49.2	67.8
						(3)	320	8：1	30	62.3	86.2
(3)	300	8：1	30	48.5	88.7
						(4)	450	10：1	6	81.5	90.6
(4)	400	10：1	6	76.2	79.1
						(5)	450	10：1	6	82.6	88.7
(5)	400	10：1	6	77.4	74.9

Application examples 4

Catalyst prepared by embodiment 4 is used for the reaction for synthesizing series fluorosurfactants alkene, and application conditions and application examples 1 are basic It is identical, as a result as shown in table 4.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 4

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	38.0	90.7
(1)	330	10：1	15	19.6	92.6
						(2)	360	4：1	16	58.1	69.9
(2)	330	4：1	16	36.5	68.3
						(3)	320	8：1	30	58.2	86.8
(3)	300	8：1	30	43.7	89.3
						(4)	450	10：1	6	79.1	90.7
(4)	400	10：1	6	72.3	79.2
						(5)	450	10：1	6	78.7	88.7
(5)	400	10：1	6	73.1	74.8

Application examples 5

Catalyst prepared by embodiment 5 is used for the reaction for synthesizing series fluorosurfactants alkene, and application conditions and application examples 1 are basic It is identical, as a result as shown in table 5.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 5

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	36.1	89.8
(1)	330	10：1	15	19.7	92.0
						(2)	360	4：1	16	57.9	72.1
(2)	330	4：1	16	36.3	69.4
						(3)	320	8：1	30	58.5	85.7
(3)	300	8：1	30	43.2	87.8
						(4)	450	10：1	6	79.5	90.4
(4)	400	10：1	6	72.1	77.9
						(5)	450	10：1	6	78.4	88.8
(5)	400	10：1	6	73.7	74.4

Application examples 6

Catalyst prepared by embodiment 6 is used for the reaction for synthesizing series fluorosurfactants alkene, and application conditions and application examples 1 are basic It is identical, as a result as shown in table 6.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 6

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	32.2	88.8
(1)	330	10：1	15	15.1	90.9
						(2)	360	4：1	16	84.3	77.7
(2)	330	4：1	16	52.1	76.0
						(3)	320	8：1	30	54.3	84.6
(3)	300	8：1	30	39.5	86.9
						(4)	450	10：1	6	75.1	89.0
(4)	400	10：1	6	68.3	76.7
						(5)	450	10：1	6	74.1	86.8
(5)	400	10：1	6	69.2	73.1

Application examples 7

Catalyst prepared by embodiment 7 is used for the reaction for synthesizing series fluorosurfactants alkene, and application conditions and application examples 1 are basic It is identical, as a result as shown in table 7.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 7

Application examples 8

Catalyst prepared by embodiment 8 is used for the reaction for synthesizing series fluorosurfactants alkene, and application conditions and application examples 1 are basic It is identical, as a result as shown in table 8.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 8

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	36.1	91.7
(1)	330	10：1	15	19.3	93.5
						(2)	360	4：1	16	57.8	70.8
(2)	330	4：1	16	36.0	68.9
						(3)	320	8：1	30	57.8	87.2
(3)	300	8：1	30	43.2	89.7
						(4)	450	10：1	6	78.7	91.8
(4)	400	10：1	6	72.6	79.6
						(5)	450	10：1	6	78.4	89.5
(5)	400	10：1	6	73.3	75.7

Application examples 9

Catalyst prepared by embodiment 9 is used for the reaction for synthesizing series fluorosurfactants alkene, and application conditions and application examples 1 are basic It is identical, as a result as shown in table 9.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 9

Application examples 10

Catalyst prepared by embodiment 10 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 10.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 10

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	34.4	90.8
(1)	330	10：1	15	17.6	92.6
						(2)	360	4：1	16	56.1	69.9
(2)	330	4：1	16	34.3	68.0
						(3)	320	8：1	30	56.1	86.3
(3)	300	8：1	30	41.5	88.8
						(4)	450	10：1	6	77.0	90.9
(4)	400	10：1	6	70.9	78.7
						(5)	450	10：1	6	76.7	88.6
(5)	400	10：1	6	71.6	74.8

Application examples 11

Catalyst prepared by embodiment 11 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 11.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 11

Application examples 12

Catalyst prepared by embodiment 12 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 12.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 12

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	36.1	90.4
(1)	330	10：1	15	19.3	92.2
						(2)	360	4：1	16	57.8	69.5
(2)	330	4：1	16	36.0	67.6
						(3)	320	8：1	30	57.8	85.9
(3)	300	8：1	30	43.2	88.4
						(4)	450	10：1	6	78.7	90.5
(4)	400	10：1	6	72.6	78.3
						(5)	450	10：1	6	78.4	88.2
(5)	400	10：1	6	73.3	74.4

Application examples 13

Catalyst prepared by embodiment 13 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 13.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 13

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	29.6	94.5
(1)	330	10：1	15	15.1	95.4
						(2)	360	4：1	16	51.0	74.3
(2)	330	4：1	16	29.2	72.4
						(3)	320	8：1	30	51.0	90.7
(3)	300	8：1	30	36.4	93.2
						(4)	450	10：1	6	71.9	95.3
(4)	400	10：1	6	65.8	83.1
						(5)	450	10：1	6	71.6	93.0
(5)	400	10：1	6	66.5	79.2

Application examples 14

Catalyst prepared by embodiment 14 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 14.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 14

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	35.7	92.0
(1)	330	10：1	15	18.4	92.2
						(2)	360	4：1	16	57.5	72.3
(2)	330	4：1	16	35.7	70.4
						(3)	320	8：1	30	57.5	88.7
(3)	300	8：1	30	42.9	91.2
						(4)	450	10：1	6	78.4	93.3
(4)	400	10：1	6	72.3	81.1
						(5)	450	10：1	6	78.1	91.0
(5)	400	10：1	6	73.0	77.2

Application examples 15

Catalyst prepared by embodiment 15 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in Table 15.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 15

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	36.0	90.5
(1)	330	10：1	15	17.8	91.6
						(2)	360	4：1	16	57.7	71.8
(2)	330	4：1	16	35.9	69.9
						(3)	320	8：1	30	57.7	88.2
(3)	300	8：1	30	43.1	90.7
						(4)	450	10：1	6	78.6	92.8
(4)	400	10：1	6	72.5	80.6
						(5)	450	10：1	6	78.3	90.5
(5)	400	10：1	6	73.2	76.7

Application examples 16

Catalyst prepared by embodiment 16 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 16.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 16

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	34.5	91.5
(1)	330	10：1	15	17.7	93.3
						(2)	360	4：1	16	56.2	70.6
(2)	330	4：1	16	34.4	68.7
						(3)	320	8：1	30	56.2	87.0
(3)	300	8：1	30	41.6	89.5
						(4)	450	10：1	6	77.1	91.6
(4)	400	10：1	6	71.0	79.4
						(5)	450	10：1	6	76.8	89.3
(5)	400	10：1	6	71.7	75.5

Application examples 17

Catalyst prepared by embodiment 17 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 17.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 17

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	37.9	91.5
(1)	330	10：1	15	20.7	91.9
						(2)	360	4：1	16	60.4	70.9
(2)	330	4：1	16	38.6	69.0
						(3)	320	8：1	30	60.4	87.3
(3)	300	8：1	30	45.8	89.8
						(4)	450	10：1	6	81.3	91.9
(4)	400	10：1	6	75.2	79.7
						(5)	450	10：1	6	81.0	89.6
(5)	400	10：1	6	75.9	75.8

Application examples 18

Catalyst prepared by embodiment 18 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 18.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 18

Application examples 19

Catalyst prepared by embodiment 19 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 19.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 19

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	37.3	90.7
(1)	330	10：1	15	19.4	91.8
						(2)	360	4：1	16	58.9	69.8
(2)	330	4：1	16	37.1	67.9
						(3)	320	8：1	30	58.9	86.2
(3)	300	8：1	30	44.3	88.7
						(4)	450	10：1	6	79.8	90.8
(4)	400	10：1	6	73.7	78.6
						(5)	450	10：1	6	79.5	88.5
(5)	400	10：1	6	74.4	74.7

Application examples 20

Catalyst prepared by embodiment 20 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 20.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 20

Application examples 21

Catalyst prepared by embodiment 21 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 21.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 21

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	37.2	91.0
(1)	330	10：1	15	18.2	92.1
						(2)	360	4：1	16	58.9	69.9
(2)	330	4：1	16	37.1	68.0
						(3)	320	8：1	30	58.9	86.3
(3)	300	8：1	30	44.3	88.8
						(4)	450	10：1	6	79.8	90.9
(4)	400	10：1	6	73.7	78.7
						(5)	450	10：1	6	79.5	88.6
(5)	400	10：1	6	74.4	74.8

Application examples 22

Catalyst prepared by embodiment 22 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 22.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 22

Application examples 23

Catalyst prepared by embodiment 23 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 23.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 23

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	30.1	91.7
(1)	330	10：1	15	13.3	93.5
						(2)	360	4：1	16	51.8	70.8
(2)	330	4：1	16	30.0	68.9
						(3)	320	8：1	30	51.8	87.2
(3)	300	8：1	30	37.2	89.7
						(4)	450	10：1	6	72.7	91.8
(4)	400	10：1	6	66.6	79.6
						(5)	450	10：1	6	72.4	89.5
(5)	400	10：1	6	67.3	75.7

Application examples 24

Catalyst prepared by embodiment 24 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 24.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 24

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	37.1	91.1
(1)	330	10：1	15	20.3	92.9
						(2)	360	4：1	16	58.8	70.2
(2)	330	4：1	16	37.0	68.3
						(3)	320	8：1	30	58.8	86.6
(3)	300	8：1	30	44.2	89.1
						(4)	450	10：1	6	79.7	91.2
(4)	400	10：1	6	73.6	79.0
						(5)	450	10：1	6	79.4	88.9
(5)	400	10：1	6	74.3	75.1

Application examples 25

Catalyst prepared by embodiment 25 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in Table 25.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 25

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	36.0	90.6
(1)	330	10：1	15	19.1	92.7
						(2)	360	4：1	16	57.3	69.9
(2)	330	4：1	16	36.3	68.4
						(3)	320	8：1	30	57.1	86.7
(3)	300	8：1	30	43.5	88.5
						(4)	450	10：1	6	78.8	90.6
(4)	400	10：1	6	72.0	79.2
						(5)	450	10：1	6	78.1	88.7
(5)	400	10：1	6	73.4	74.9

Application examples 26

Catalyst prepared by embodiment 26 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 26.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 26

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	36.3	90.8
(1)	330	10：1	15	19.5	92.6
						(2)	360	4：1	16	58.0	69.9
(2)	330	4：1	16	36.2	68.0
						(3)	320	8：1	30	58.0	86.3
(3)	300	8：1	30	43.4	88.8
						(4)	450	10：1	6	78.9	90.9
(4)	400	10：1	6	72.8	78.7
						(5)	450	10：1	6	78.6	88.6
(5)	400	10：1	6	73.5	74.8

Application examples 27

Catalyst prepared by embodiment 27 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 27.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 27

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	35.6	90.8
(1)	330	10：1	15	18.8	92.6
						(2)	360	4：1	16	57.3	69.9
(2)	330	4：1	16	35.5	68.0
						(3)	320	8：1	30	57.3	86.3
(3)	300	8：1	30	42.7	88.8
						(4)	450	10：1	6	78.2	90.9
(4)	400	10：1	6	72.1	78.7
						(5)	450	10：1	6	77.9	88.6
(5)	400	10：1	6	72.8	74.8

Application examples 28

Catalyst prepared by embodiment 28 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 28.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 28

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	35.4	90.9
(1)	330	10：1	15	18.6	92.7
						(2)	360	4：1	16	57.1	70.0
(2)	330	4：1	16	35.3	68.1
						(3)	320	8：1	30	57.1	86.4
(3)	300	8：1	30	42.5	88.9
						(4)	450	10：1	6	78.0	91.0
(4)	400	10：1	6	71.9	78.8
						(5)	450	10：1	6	77.7	88.7
(5)	400	10：1	6	72.6	74.9

Application examples 29

Catalyst prepared by embodiment 29 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 29.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 29

Application examples 30

Catalyst prepared by embodiment 30 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 30.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 30

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	43.1	90.7
(1)	330	10：1	15	26.5	92.9
						(2)	360	4：1	16	85.0	83.9
(2)	330	4：1	16	53.2	78.1
						(3)	320	8：1	30	65.0	86.2
(3)	300	8：1	30	50.4	88.8
						(4)	450	10：1	6	85.9	90.7
(4)	400	10：1	6	79.8	78.6
						(5)	450	10：1	6	85.6	88.8
(5)	400	10：1	6	80.5	74.9

Application examples 31

Catalyst prepared by embodiment 31 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 31.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 31

Application examples 32

Catalyst prepared by embodiment 32 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 32.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 32

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	35.2	91.4
(1)	330	10：1	15	18.4	93.2
						(2)	360	4：1	16	56.9	70.5
(2)	330	4：1	16	35.1	68.6
						(3)	320	8：1	30	56.9	86.9
(3)	300	8：1	30	42.3	89.4
						(4)	450	10：1	6	77.8	91.5
(4)	400	10：1	6	71.7	79.3
						(5)	450	10：1	6	77.5	89.2
(5)	400	10：1	6	72.4	75.4

Application examples 33

Catalyst prepared by embodiment 33 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 33.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 33

Application examples 34

Catalyst prepared by embodiment 34 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 34.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 34

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	34.9	91.9
(1)	330	10：1	15	18.1	93.7
						(2)	360	4：1	16	56.6	71.0
(2)	330	4：1	16	34.8	69.1
						(3)	320	8：1	30	56.6	87.4
(3)	300	8：1	30	42.0	89.9
						(4)	450	10：1	6	77.5	92.0
(4)	400	10：1	6	71.4	79.8
						(5)	450	10：1	6	77.2	89.7
(5)	400	10：1	6	72.1	75.9

Application examples 35

Catalyst prepared by embodiment 35 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 35.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 35

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	34.6	92.0
(1)	330	10：1	15	17.8	93.8
						(2)	360	4：1	16	56.3	71.1
(2)	330	4：1	16	34.5	69.2
						(3)	320	8：1	30	56.3	87.5
(3)	300	8：1	30	41.7	90.0
						(4)	450	10：1	6	77.2	92.1
(4)	400	10：1	6	71.1	79.9
						(5)	450	10：1	6	76.9	89.8
(5)	400	10：1	6	71.8	76.0

Application examples 36

Catalyst prepared by embodiment 36 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 36.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 36

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	34.5	92.2
(1)	330	10：1	15	17.7	94.0
						(2)	360	4：1	16	56.2	71.3
(2)	330	4：1	16	34.4	69.4
						(3)	320	8：1	30	56.2	87.7
(3)	300	8：1	30	41.6	90.2
						(4)	450	10：1	6	77.1	92.3
(4)	400	10：1	6	71.0	80.1
						(5)	450	10：1	6	76.8	90.0
(5)	400	10：1	6	71.7	76.2

Application examples 37

Catalyst prepared by embodiment 37 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 37.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 37

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	34.3	90.4
(1)	330	10：1	15	17.5	92.2
						(2)	360	4：1	16	56.0	69.5
(2)	330	4：1	16	34.2	67.6
						(3)	320	8：1	30	56.0	85.9
(3)	300	8：1	30	41.4	88.4
						(4)	450	10：1	6	76.9	90.5
(4)	400	10：1	6	70.8	78.3
						(5)	450	10：1	6	76.6	88.2
(5)	400	10：1	6	71.5	74.4

Application examples 38

Catalyst prepared by embodiment 38 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 38.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 38

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	34.2	92.1
(1)	330	10：1	15	17.4	93.9
						(2)	360	4：1	16	55.9	71.2
(2)	330	4：1	16	34.1	69.3
						(3)	320	8：1	30	55.9	87.6
(3)	300	8：1	30	41.3	90.1
						(4)	450	10：1	6	76.8	92.2
(4)	400	10：1	6	70.7	80.0
						(5)	450	10：1	6	76.5	89.9
(5)	400	10：1	6	71.4	76.1

Application examples 39

Catalyst prepared by embodiment 39 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 39.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 39

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	34.0	92.3
(1)	330	10：1	15	17.2	94.1
						(2)	360	4：1	16	55.7	71.4
(2)	330	4：1	16	33.9	69.5
						(3)	320	8：1	30	55.7	87.8
(3)	300	8：1	30	41.1	90.3
						(4)	450	10：1	6	76.6	92.4
(4)	400	10：1	6	70.5	80.2
						(5)	450	10：1	6	76.3	90.1
(5)	400	10：1	6	71.2	76.3

Application examples 40

Catalyst prepared by embodiment 40 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 40.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 40

Application examples 41

Catalyst prepared by embodiment 41 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 41.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 41

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	36.1	92.8
(1)	330	10：1	15	19.3	94.6
						(2)	360	4：1	16	57.8	71.9
(2)	330	4：1	16	36.0	70.0
						(3)	320	8：1	30	57.8	88.3
(3)	300	8：1	30	43.2	90.8
						(4)	450	10：1	6	78.7	92.9
(4)	400	10：1	6	72.6	80.7
						(5)	450	10：1	6	78.4	90.6
(5)	400	10：1	6	73.3	76.8

Application examples 42

Catalyst prepared by embodiment 42 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 42.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 42

Application examples 43

Catalyst prepared by embodiment 43 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 43.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 43

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	35.8	93.1
(1)	330	10：1	15	19.0	94.9
						(2)	360	4：1	16	57.5	72.2
(2)	330	4：1	16	35.7	70.3
						(3)	320	8：1	30	57.5	88.6
(3)	300	8：1	30	42.9	91.1
						(4)	450	10：1	6	78.4	93.2
(4)	400	10：1	6	72.3	81.0
						(5)	450	10：1	6	78.1	90.9
(5)	400	10：1	6	73.0	77.1

Application examples 44

Catalyst prepared by embodiment 44 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 44.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 44

Application examples 45

Catalyst prepared by embodiment 45 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 45.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 45

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	42.8	91.6
(1)	330	10：1	15	26.0	92.1
						(2)	360	4：1	16	85.1	84.0
(2)	330	4：1	16	52.8	77.5
						(3)	320	8：1	30	64.5	85.6
(3)	300	8：1	30	49.9	88.3
						(4)	450	10：1	6	85.6	89.8
(4)	400	10：1	6	79.4	78.0
						(5)	450	10：1	6	85.4	88.2
(5)	400	10：1	6	80.1	74.4

Application examples 46

Catalyst prepared by embodiment 46 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 46.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 46

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	28.2	90.7
(1)	330	10：1	15	12.6	92.4
						(2)	360	4：1	16	47.5	68.9
(2)	330	4：1	16	23.1	67.6
						(3)	320	8：1	30	48.8	85.7
(3)	300	8：1	30	24.1	88.1
						(4)	450	10：1	6	68.2	90.2
(4)	400	10：1	6	57.4	77.9
						(5)	450	10：1	6	65.5	87.9
(5)	400	10：1	6	58.7	74.5

Application examples 47

Catalyst prepared by embodiment 47 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 47.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 47

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	38.6	90.0
(1)	330	10：1	15	21.7	91.5
						(2)	360	4：1	16	70.9	68.9
(2)	330	4：1	16	48.6	67.1
						(3)	320	8：1	30	61.7	85.5
(3)	300	8：1	30	47.9	88.0
						(4)	450	10：1	6	80.9	89.9
(4)	400	10：1	6	75.6	78.4
						(5)	450	10：1	6	82.0	88.0
(5)	400	10：1	6	76.8	74.2

Application examples 48

Catalyst prepared by embodiment 48 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 48.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 48

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	37.4	90.0
(1)	330	10：1	15	19.0	91.9
						(2)	360	4：1	16	57.5	69.2
(2)	330	4：1	16	35.9	67.6
						(3)	320	8：1	30	57.6	86.1
(3)	300	8：1	30	43.1	88.6
						(4)	450	10：1	6	78.5	90.0
(4)	400	10：1	6	71.7	78.5
						(5)	450	10：1	6	78.1	88.0
(5)	400	10：1	6	72.5	74.1

Application examples 49

Catalyst prepared by embodiment 49 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 49.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 49

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	35.5	89.1
(1)	330	10：1	15	19.1	91.3
						(2)	360	4：1	16	57.3	71.4
(2)	330	4：1	16	35.7	68.7
						(3)	320	8：1	30	57.9	85.0
(3)	300	8：1	30	42.6	87.1
						(4)	450	10：1	6	78.9	89.7
(4)	400	10：1	6	71.5	77.2
						(5)	450	10：1	6	77.8	88.1
(5)	400	10：1	6	73.1	73.7

Application examples 50

Catalyst prepared by embodiment 50 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 50.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 50

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	31.6	88.1
(1)	330	10：1	15	14.5	90.2
						(2)	360	4：1	16	83.7	77.0
(2)	330	4：1	16	51.5	75.3
						(3)	320	8：1	30	53.7	83.9
(3)	300	8：1	30	38.9	86.2
						(4)	450	10：1	6	74.5	88.3
(4)	400	10：1	6	67.7	76.0
						(5)	450	10：1	6	73.5	86.1
(5)	400	10：1	6	68.6	72.4

Application examples 51

Catalyst prepared by embodiment 51 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 51.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 51

Application examples 52

Catalyst prepared by embodiment 52 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 52.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 52

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	35.5	91.0
(1)	330	10：1	15	18.7	92.8
						(2)	360	4：1	16	57.2	70.1
(2)	330	4：1	16	35.4	68.2
						(3)	320	8：1	30	57.2	86.5
(3)	300	8：1	30	42.6	89.0
						(4)	450	10：1	6	78.1	91.1
(4)	400	10：1	6	72.0	78.9
						(5)	450	10：1	6	77.8	88.8
(5)	400	10：1	6	72.7	75.0

Application examples 53

Catalyst prepared by embodiment 53 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 53.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 53

Application examples 54

Catalyst prepared by embodiment 54 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 54.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 54

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	33.8	90.1
(1)	330	10：1	15	17.0	91.9
						(2)	360	4：1	16	55.5	69.2
(2)	330	4：1	16	33.7	67.3
						(3)	320	8：1	30	55.5	85.6
(3)	300	8：1	30	40.9	88.1
						(4)	450	10：1	6	76.4	90.2
(4)	400	10：1	6	70.3	78.0
						(5)	450	10：1	6	76.1	87.9
(5)	400	10：1	6	71.0	74.1

Application examples 55

Catalyst prepared by embodiment 55 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 55.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 55

Application examples 56

Catalyst prepared by embodiment 56 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 56.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 56

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	22.7	93.9
(1)	330	10：1	15	37.2	90.3
						(2)	360	4：1	16	20.4	92.1
(2)	330	4：1	16	58.9	69.4
						(3)	320	8：1	30	37.1	67.5
(3)	300	8：1	30	58.9	85.8
						(4)	450	10：1	6	44.3	88.3
(4)	400	10：1	6	79.8	90.4
						(5)	450	10：1	6	73.7	78.2
(5)	400	10：1	6	79.5	88.1

Application examples 57

Catalyst prepared by embodiment 57 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and application examples 1 It is essentially identical, as a result as shown in table 57.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 57

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	33.9	92.7
(1)	330	10：1	15	17.1	94.5
						(2)	360	4：1	16	55.6	71.8
(2)	330	4：1	16	33.8	69.9
						(3)	320	8：1	30	55.6	88.2
(3)	300	8：1	30	41.0	90.7
						(4)	450	10：1	6	76.5	92.8
(4)	400	10：1	6	70.4	80.6
						(5)	450	10：1	6	76.2	90.5
(5)	400	10：1	6	71.1	76.7

Fluorine containing olefine selectively refers to the ratio of target product, and generation E-HFO-1225ye, Z-HFO- are referred to for reaction (3) 1225ye selective summation, the selectivity for referring to generation E-HFO-1234ze, Z-HFO-1234ze for reaction (4) and (5) is total With, other reaction be simple target product selectivity

Application examples 58

Catalyst prepared by embodiment 58 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 58.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 58

Reaction	Temperature/DEG C	HF：Alkenyl halide/mol ratio	Time of contact/s	Alkenyl halide conversion ratio/%	Fluorine containing olefine selectivity/%
						(1)	390	10：1	15	42.5	90.0
(1)	330	10：1	15	25.9	92.2
						(2)	360	4：1	16	84.4	83.2
(2)	330	4：1	16	52.6	77.4
						(3)	320	8：1	30	64.4	85.5
(3)	300	8：1	30	49.8	88.1
						(4)	450	10：1	6	85.3	90.0
(4)	400	10：1	6	79.2	77.9
						(5)	450	10：1	6	85.0	88.1
(5)	400	10：1	6	79.9	74.2

Claims

1. a kind of non-chrome catalysts, the non-chrome catalysts are made up of non-chromium ion and auxiliary agent, non-chromium ion be divalence tungsten ion, Trivalent tungsten ion, tetravalence tungsten ion, pentavalent tungsten ion, sexavalence tungsten ion, divalence molybdenum ion, trivalent molybdenum ion, tetravalence molybdenum ion, One or several kinds in pentavalent molybdenum ion, sexavalence molybdenum ion, auxiliary agent be Al, Mg, Ni, Co, Ti, Zr, V, Fe, Zn, In, Cu, Ag, At least one of Cd, Hg, Ga, Sn, Pb, Mn, Ba, Re, Sc, Sr, Ru, Nb, Ta, Ca, Ce, Sb, Tl, Hf metal is several, And the quality percentage composition of non-chromium ion and auxiliary agent is 60%~100% and 0~40%, the preparation method of the catalyst is as follows：

(1) according to the mass percent of non-chromium ion and auxiliary agent, the precursor of the precursor of non-chromium ion and auxiliary agent is well mixed, pressed Type is made, catalyst precarsor is obtained；

(2) catalyst precarsor for obtaining step (1), carries out roasting 6~15 hours in 300 DEG C~500 DEG C under nitrogen atmosphere； It is 1 in the amount ratio of material in 200 DEG C~400 DEG C：After 2 hydrogen fluoride is activated 6~15 hours with the mixed gas that nitrogen is constituted, Non- chrome catalysts are made.

2. non-chrome catalysts according to claim 1, the precursor of the non-chromium ion be wolframic acid, ammonium tungstate, ammonium metatungstate, Ammonium paratungstate, three two tungsten of oxidation, tungsten dioxide, tungsten pentoxide, dihydro tungsten oxide, three hydroxide tungsten, tungsten tetrahydroxide, pentahydro- Tungsten oxide, hexahydro tungsten oxide, molybdenum sesquioxide, molybdenum dioxide, molybdenum hemipentoxide, molybdenum trioxide, two molybdenum hydroxides, three hydroxides In molybdenum, four molybdenum hydroxides, five molybdenum hydroxides, hexahydro molybdenum oxide, positive ammonium molybdate, ammonium dimolybdate, ammonium tetramolybdate or ammonium heptamolybdate It is at least one or several；During the precursor of auxiliary agent is oxide, hydroxide, nitrate, acetate or the carbonate of metal It is at least one or several.

3. non-chrome catalysts according to claim 2, the precursor of the non-chromium ion is ammonium metatungstate or ammonium dimolybdate, institute The precursor for stating auxiliary agent is the compound containing manganese or scandium or rhenium or nickel or cobalt, and the quality percentage of non-chromium ion and assistant metal element contains Amount is respectively 80%~95% and 5~20%.

4. non-chrome catalysts according to claim 3, the precursor of the auxiliary agent is nitrate.

5. non-chrome catalysts according to claim 4, the precursor of the non-chrome catalysts is ammonium metatungstate and nickel nitrate Mixture, wherein, the mass percent composition of tungsten ion and nickel element is 90% and 10%；Or

The precursor of described non-chrome catalysts is the mixture of ammonium metatungstate and scandium nitrate, wherein, the matter of tungsten ion and scandium element It is 90% and 10% to measure percentage composition；Or

The precursor of described non-chrome catalysts is the mixture of ammonium metatungstate and nitric acid rhenium, wherein, the matter of tungsten ion and rhenium element It is 90% and 10% to measure percentage composition；Or

The precursor of described non-chrome catalysts is the mixture of ammonium dimolybdate and nickel nitrate, wherein, the matter of molybdenum ion and nickel element It is 90% and 10% to measure percentage；Or

The precursor of described non-chrome catalysts is the mixture of ammonium dimolybdate and cobalt nitrate, wherein, the matter of molybdenum ion and cobalt element It is 90% and 10% to measure percentage.

6. the preparation method of any described non-chrome catalysts of claim 1-5, using the following steps：

7. application of any non-chrome catalysts of claim 1-6 in exchange chloride for fluoride.

8. application according to claim 7, the exchange chloride for fluoride is high temperature gas phase reaction, wherein raw material is chloride halogen For alkene and hydrogen fluoride gas, product is Fluorine containing olefine, and the pyroreaction is to be reacted at 300 DEG C -450 DEG C.

9. application according to claim 8, the pyroreaction is to be reacted at 400-450 DEG C.

10. application according to claim 9, the alkenyl halide is ring-CF₂CF₂CF₂CCl=CCl, prepare ring- CF₂CF₂CF₂CF=CCl；

Or the alkenyl halide is 2- chloro-3,3,3 ,-trifluoropropenes, prepares 2,3,3,3- tetrafluoropropenes；

Or the alkenyl halide is E/Z-1- chloro- 2,3,3,3- tetrafluoropropenes prepare E/Z-1,2,3,3,3- pentafluoropropenes；

Or the alkenyl halide is E-1- chloro-3,3,3 ,-trifluoropropenes, prepares E/Z-1,3,3,3- tetrafluoropropenes；

Or the alkenyl halide is Z-1- chloro-3,3,3 ,-trifluoropropenes, prepares E/Z-1,3,3,3- tetrafluoropropenes.